Alkylidene bisphenol phosphites and phosphates having 2,2,6,6-tetramethyl piperidinyl groups and synthetic resin composition

ABSTRACT

Alkylidene bisphenol phosphites and phosphates having 2,2,6,6-tetramethyl piperidinyl groups are provided having the formula: ##STR1## wherein: R 1  is alkyl having from one to about twelve carbon atoms; 
     R 2 , R 3  and R 4  are each selected from the group consisting of hydrogen and alkyl having from one to about twelve carbon atoms; 
     m is 0 or 1; 
     n is 0 or 1; 
     X is selected from the group consisting of ##STR2## wherein: R 5  is selected from the group consisting of hydrogen, oxyl O 2 , alkyl having from one to about twelve carbon atoms; arylalkyl having from seven to about eighteen carbon atoms; 2,3-epoxypropyl, acyl having from one to about eight carbon atoms and ##STR3##  in which R 6  is selected from the group consisting of hydrogen, alkyl having from one to about twelve carbon atoms and phenyl, and Y 1  is selected from the group consisting of hydrogen; acyl having from one to about twelve carbon atoms; and ##STR4## Z 1  is selected from the group consisting of ##STR5##  wherein R 7  is alkyl from one to about twelve carbon atoms; and ##STR6## wherein: R 6  is selected from the group consisting of hydrogen, alkyl having from one to about twelve carbon atoms and phenyl; and 
     Z 2  is selected from the group consisting of ##STR7##  in which R 7  is alkyl having from one to about twelve carbon atoms; R 6  is alkylene having from one to about eight carbon atoms and 
     Y 2  is selected from the group consisting of hydrogen and acyl having from one to about eight carbon atoms.

Synthetic resins such as polyethene, polypropylene, polystyrene andpolyvinyl chloride show a strong tendency to deteriorate in physicalproperties at elevated temperatures and when exposed to ultravioletlight. The deterioration is evidenced by, among other things, a decreasein viscosity, a tendency to become brittle, and discoloration. Thisdeterioration can be accompanied by distortion, cracking, and powderingof the material. To overcome these difficulties, many stabilizers havebeen proposed for combination with synthetic resins.

No single stabilizer has proved adequate, and combinations ofstabilizers are consequently used almost exclusively. Most stabilizedsynthetic resins on the market contain one or more of such stabilizercombinations. The deterioration appears to be due to a combination offactors, and a combination of stabilizers is therefore more capable ofcoping with the various types of deterioration. However, the retentionof good physical properties over long periods of time remains ratherdifficult to achieve.

Of the many stabilizer systems that have been proposed for polyolefins,one particularly satisfactory stabilizer system is described in U.S.Pat. No. 3,255,136, patented June 7, 1966 to Arthur Hecker, Otto S.Kauder and Norman Perry. This stabilizer system comprises threestabilizers: an organic mono- or polyhydric phenol, an organicphosphite, and a thiodipropionic acid ester. An additional fourthingredient, which is preferred but not essential, is a polyvalent metalsalt of an organic acid. These three and four stabilizers together givean enhanced stabilization which is not obtainable from any of themalone, or in combinations of two.

In these combinations, the phenol alone gives an improved resistance toembrittlement and reduction in melt viscosity of polypropylene atelevated temperatures, but little assistance as to maintenance of color.The phosphite alone is a rather poor stabilizer in preventingdeterioration in the first two properties, but it does assist inresisting discoloration. The two together are worse than the phenolalone in every respect except color, which is intermediate.

The thiodipropionic acid ester by itself only improves resistance toembrittlement. The polyvalent metal salt of an organic acid by itselfonly prevents discoloration. In combinations with the phenol, the coloris worse than with the salt alone, and combinations with phosphite only,discoloration is prevented. The effectiveness of all three or fouringredients taken together against all of these types of deteriorationis therefore particularly surprising.

The organic phosphite can be any organic phosphite having the formula(RA)₃ --P, in which A can be oxygen or sulfur or a mixture of the same,and R is aryl, alkyl, cycloalkyl, aralkyl or aralkaryl in anycombination. A variety of tris-alkaryl phosphites are disclosed, such astris-(tertiary-octyl-phenyl)phosphite andtris-(tertiary-nonyl-phenyl)phosphite, but no tris-(alkaryl)phosphiteshaving more than one alkyl group per phenyl group.

Organic phosphites have been widely used as stabilizers for polyolefinsand similar polymeric materials, particularly polyvinyl chloride, andmany different types of phosphites, some of rather complex structure,have been proposed. U.S. Pat. Nos. 3,255,136 and 3,655,832 havesuggested organic phosphite-phenol transesterification products, thepreferred phenol being a bis-phenol. Other types oftris-(alkaryl)phosphites esters have been disclosed in U.S. Pat. Nos.2,220,113; 2,220,845; 2,246,059; 2,419,354; 2,612,488; 2,732,365;2,733,226; and 2,877,259. Additional tris-(alkaryl)phosphites aredisclosed in U.S. Pat. No. 3,167,526 to Nicholson, patented Jan. 26,1965; U.S. Pat. No. 3,061,583 to Huhn and Sheets, patented Oct. 30,1962; U.S. Pat. No. 3,829,396 to Oakes and Cross, patented Aug. 13,1974; French Pat. Nos. 1,496,563 to U.S. Rubber Company, delivre Aug.21, 1967, and 1,497,390 to Ethyl Corporation, delivre Aug. 28, 1967; andBritish Pat. Nos. 1,058,977 published Feb. 15, 1967, to Hooker ChemicalCorporation and 1,143,375, published Feb. 19, 1969, to Uniroyal Inc.

Oakes et al disclose bis-(2,4-di-tertiary-butyl-phenol)cyclohexylphosphite and 2,4-di-(tertiary butyl)phenyl dicyclohexyl phosphite,which are liquids.

French Pat. No. 1,496,563 described phosphites derived from2,6-di-tertiary-butyl-hydroquinone and2,5-di-tertiary-butyl-hydroquinone, and it is suggested that they can beused with thiodipropionic acid esters of olefin polymers.

British Pat. No. 1,143,375 has a similar disclosure;tris-(2,5-di-tertiary-butyl-4-hydroxy-phenyl)phosphite is disclosed.

British Pat. No. 1,058,977 discloses 2,4,6-tri-substituted arylphosphites, the substituents including tertiary-butyl groups.

French Pat. No. 1,497,390 disclosestris-(3,5-di-alkyl-4-hydroxy-phenyl)phosphites, as well astris-(3-isopropyl-5-tertiary-butyl-phenyl)phosphite.

Kuriyama et al U.S. Pat. No. 3,558,554 patented Jan. 26, 1971, providesolefin polymer compositions containing as a stabilizer anorganophosphite having the general formula: ##STR8## wherein R₁ and R₂each represents a member selected from the group consisting ofsubstituted and unsubstituted alkyl, cycloalkyl, aryl, alkaryl, aralkyl,and aliphatic thio ether groups and R₃, R₄ and R₅ each represents amember selected from the group consisting of hydrogen and alkyl,cycloalkyl, aryl, alkaryl, and aralkyl groups, at least one of said R₃and R₄ being a tertiary butyl group.

Suitable organo phosphites include, for example, di-n-butyl(2-t-butyl-cresyl)phosphite, di-n-hexyl(2-t-butyl-m-cresyl)phosphite,di-n-hexyl(2-t-butyl-p-cresyl)phosphite,di-n-octyl(2-t-butyl-p-cresyl)phosphite,di-n-butyl-3,4-di-t-butyl-phenyl)phosphite,di-n-butyl-(2,6-di-t-butyl-p-cresyl)phosphite,di-phenyl(2-t-butyl-p-cresyl)phosphite,tri-(2-t-butyl-p-cresyl)phosphite,di(ethylthioethyl)-(2-t-butyl-p-cresyl)phosphite,di(octylthioethyl)(2-t-butyl-p-cresyl)phosphite, andtri(2,4-di-t-butyl-phenyl)phosphite.

Many organic phosphites have been proposed as stabilizers for polyvinylchloride resins, and are employed either alone or in conjunction withother stabilizing compounds, such as polyvalent metal salts of fattyacids and alkyl phenols. Such phosphite stabilizers normally containalkyl or aryl radicals in sufficient number to satisfy the threevalences of the phosphite, and typical phosphites are described in thepatent literature, for example, W. Leistner et al., U.S. Pat. Nos.2,564,646 of Aug. 14, 1951, 2,716,092 of Aug. 23, 1955, and 2,997,454 ofAug. 2, 1961.

Organic phosphites have also been added as stabilizers in amounts of0.01 to 1%, preferably 0.05% to 0.2% by weight, to high molecular weightpolycarbonate plastics, for example the polycarbonate of2,2'-bis(4-hydroxyphenyl)propane of molecular weight 10,000 and up toover 50,000 as disclosed by G. Fritz in U.S. Pat. No. 3,305,520 of Feb.21, 1967.

A. Hecker in U.S. Pat. No. 2,860,115 of Nov. 11, 1958 disclosescompositions of organic phosphites with metal salts of carboxylic acidsused in olefin polymers.

Phosphites are also employed in conjunction with other stbilizers suchas a polyhydric phenol in the stabilization of polypropylene and othersynthetic resins against degradation upon heating or ageing underatmospheric conditions. The polyhydric phenol is thought to function asan antioxidant in such combinations. Disclosures by R. Werkheiser, U.S.Pat. Nos. 2,726,226 of Dec. 6, 1975; I. Salyer et al, 2,985,617 of May23, 1961; L. Friedman, 3,039,993 of June 19, 1962; W. Nudenberg,3,080,338 of Mar. 5, 1963; C. Fuchsman, 3,082,187 of Mar. 19, 1963; H.Orloff et al, 3,115,465 of Dec. 24, 1963; A. Nicholson, 3,167,526 ofJan. 26, 1965; A. Hecker et al, 3,149,093 of Sept. 15, 1964, 3,244,650of Apr. 5, 1966 and 3,225,136 and 3,255,151 of June 7, 1966; C. Bawn,3,352,820 of Nov. 14, 1967; D. Miller, 3,535,277 of Oct. 20, 1970; J.Casey, 3,568,657 of June 22, 1971; C. Abramoff 3,856,728 of Dec. 24,1974; M. Minagawa, 3,869,423 of Mar. 4, 1975 and 3,907,517 of Sept. 23,1975; and British Pat. Nos. 846,684, 851,670, and 866,883 arerepresentative of stabilizer combinations including organic phosphites,polyhydric phenols, and other active ingredients.

The importance of organic phosphites as stabilizers for synthetic resinshas led to the development of a large variety of special phosphitesintended to provide improved stabilizing effectiveness and compatabilityand ease of compounding with the resin and with other stabilizerscommonly used. However, the phosphites which have been proposed have notbeen entirely successful, partly because of their complicated structure,which makes them costly to prepare, and partly because of theirdifficulty of preparation.

Among these special phosphites, L. Friedman, U.S. Pat. No. 3,047,608 ofJuly 31, 1962 discloses a class of bisphosphites having the formula:##STR9## in which R₁, R₂, R₃ and R₄ are alkyl or aryl and Z is --CH₂ CH₂SCH₂ CH₂ O--, --C₂ CH₂ SO₂ C₂ CH₂ --(--CH₂ CH₂ O--)_(x) or --(CHCH₃CH₂)_(x) where x is at least two, and in U.S. Pat. No. 3,053,878 ofSept. 11, 1962 a class of linear phosphite polymers from the formula:##STR10## in which Q is the alkylene or arylene portion of a dihydricalcohol or dihydric phenol.

R. Morris et al in U.S. Pat. No. 3,112,286 of Nov. 26, 1963 disclosesphosphites having the formula: ##STR11## in which R represents a bulkyhydrocarbon group such as t-butyl, t-amyl, t-hexyl, cyclohexyl,t-pentyl, t-octyl, phenyl and the like;

R₁ represents hydrogen and R;

R₃ represents an alkyl group from six to twenty carbon atoms which ispreferably in the meta or para position;

x represents a number of from 1 to 3 inclusive;

y represents a number of from 0 to 2 inclusive and the sum of thenumerical value of x+y is always exactly 3.

D. Brown, U.S. Pat. No. 3,297,631 of Jan. 10, 1967 disclosescondensation products of phosphorus compounds with bisphenols andtrisphenols which may be represented by the structures: ##STR12## where:X is selected from the following: >P--OR'; >P--R'; ##STR13## and Y isselected from the following: --P(OR')₂ ; ##STR14## R is hydrogen, alkylof one to sixteen carbon atoms or aryl or a combination of these; R' isalkyl of one to sixteen carbon atoms or aryl, and R" is alkylidene ofone to sixteen carbon atoms or an aryl-substituted alkylidene.

C. Baranauckas, U.S. Pat. No. 3,305,608 of Feb. 21, 1967, disclosesphenolic phosphites useful as polymer stabilizers prepared by reacting atriorganophosphite, a polyol, and an aromatic material having two to sixphenolic hydroxyl groups at 60° to 180° C. in specified proportions.

C. Brindell, U.S. Pat. No. 3,412,064 of Nov. 19, 1968 discloses phenolicphosphites represented by the general formula: ##STR15## where x is from1 to 3, y and z each from 0 to 2, x+y+z=3, R is hydrogen or alkyl and Yis hydroxyl or a group of the formula: ##STR16## where R is hydrogen oralkyl.

M. Larrison, U.S. Pat. No. 3,419,524 of Dec. 31, 1968, disclosesphosphites useful as polymer stabilizers having the formula: ##STR17##where R₁, R₂, R₄, R₆ and R₇ are aryl or haloaryl, and R₃ and R₅ are apolyalkylidene glycol or an alkylidene bisphenol or a hydrogenatedalkylidene bisphenol or a ring-halogenated alkylidene bisphenol fromwhich the two terminal hydrogens have been removed.

O. Kauder et al, U.S. Pat. No. 3,476,699 of Nov. 4, 1969 and U.S. Pat.No. 3,655,832 of Apr. 11, 1972 discloses organic phosphites containing afree phenolic hydroxyl group and defined by the formula: ##STR18##wherein Z is selected from the group consisting of hydrogen andaliphatic, cycloaliphatic, aromatic, heterocyclic and (Ar)_(p) --Y--Argroups, taken in sufficient number to satisfy the valences of the twophosphite oxygen atoms; Y is a polyvalent linking group selected fromthe group consisting of oxygen; aliphatic, cycloaliphatic and aromatichydrocarbon groups attached to each Ar group through a carbon atom not amember of an aromatic ring; oxyaliphatic; thioaliphatic,oxycycloaliphatic, thiocycloaliphatic; heterocyclic, oxyheterocyclic,thioheterocyclic, carbonyl, sulfinyl; and sulfonyl groups; Ar is aphenolic nucleus which can be phenyl or a polycarbocyclic group havingcondensed or separate phenyl rings; each Ar group is either connectedthrough an oxygen atom to a phosphite group or contains a free phenolichydroxyl group, or both; and p is a number, one or greater, andpreferably from one to four, which defines the number of Ar groupslinked to Y.

L. Friedman, U.S. Pat. No. 3,516,963 of June 23, 1970 disclosesphosphites having the formula: ##STR19## where R is alkyl, alkenyl,aryl, aralkyl, haloaryl, haloalkyl or ##STR20## and n is an integer ofat least 1. n can be 2, 3, 4, 5, 6, 7, 8, 10, 50, 100 or even more.

D. Brown et al in U.S. Pat. Nos. 3,510,507 of May 5, 1970 and 3,691,132of Sept. 12, 1972 discloses polyolefins stabilized with polyphosphites,polyphosphates, polyphosphonites, polyphosphonates, polyborates,polycarbonates, and polysilanes which are condensation products of a4,4'-bisphenol with a condensing or linking agent which may be of theester type, such as the esters of triaryl or mixed aryl-alkyl compounds,or the acid halide type. Brown's condensation product stablizers havemolecular weights between 600 and 8000 or higher and are described bythe structural formula: ##STR21## where X is selected from the groupconsisting of ##STR22## --C--C, and C--A--C-- where A is a C₁ to C₁₆alkylene or an arylene; R', R", R"', and R"" are selected from the groupconsisting of hydrogen, C₁ to C₁₈ alkyls, and an aryl group; Y isselected from the group of ##STR23## where R is hydrogen, a C₁ to C₁₈alkyl or aryl; ##STR24## where m is 0 to 10, preferably 4 to 8,##STR25## where A' is (CH₂)_(n) --S--(CH₂)_(n) or --(CH₂)_(n)--S--(CH₂)_(m) --S--(CH₂)_(n) where n is 0 to 10, preferably 2 and m is0 to 10, preferaby 5; ##STR26## where R is an alkyl, preferably methyl,and Z is ##STR27## where R', R", R'", R"", and X correspond respectivelyto the R', R", R'", R"", and X previously selected when n has a valuefrom 1 to 15, or may be derived from the compound used to introduce Yinto the product when n has a value from 2 to 15, for example, --R or--OR where R is hydrogen, an alky, or aryl. When Y in the formula ofBown's stabilizer is ##STR28## the stabilizer is a type of hydroxyarylphosphite. Similarly, when Y in the formula is ##STR29## the stabilizeris a hydroxyaryl carbonate.

Bown's condensation products are described as especially effective inhigh molecular weight solid polyolefins when used together with adialkyl sulfide costabilizer such as dilauryl thiodipropionate,distearyl thiodipropionate, ditridecyl thiodipropionate, dicetylsulfide, bis(tetradecylmercapto)paraxylylene, and 10,24-dithiotetracontane.

J. Floyd et al in German published application No. 2505071 of Aug. 14,1975 abstracted in Chemical Abstracts 1976. Volume 84, abstract No.5945f, discloses low molecular weight polycarbonate esters of bisphenolssuch as 2,2-bis(3-t-butyl-4-hydroxyphenylpropane) and 4,4'-butylidenebis(6-t-butyl-3-methylphenol) prepared in such a way as to contain fewor no free phenolic hydroxyl groups as being highly effective heat andlight stabilizers for polyolefins and giving a synergistic effect withdistearyl thiodipropionate, tris(nonylphenyl)phosphite, and distearylpentaerythritol diphosphite.

U.S. Pat. No. 4,252,750 to Buysch et al, patented Feb. 24, 1981,provides phosphorous acid esters corresponding to the general formula##STR30## wherein R₂ is a benzyl, α-methylbenzyl, α,α-dimethylbenzyl,cyclopentyl or cyclohexyl radical;

R₁ is a C₁ -C₉ alkyl, a C₅ -C₆ cycloalkyl, a C₇ -C₉ aralkyl or a C₆ -C₁₀aryl radical;

Y is a sulphur atom or a group HC--R₃, in which R₃ is a hydrogen atom aC₁ -C₆ alkyl, a cyclohexyl or cyclohexenyl radical;

X is a hydrogen atom, an optionally substituted single-bond to four-bondstraight-chain or branched-chain C₁ -C₁₈ aliphatic radical, A C₇ -C₁₈aralkyl radical or a C₆ -C₁₈ aromatic radical, each of which radicalsmay optionally contain olefinic double bonds and/or hetero atoms,preferably N, O and/or S atoms, and

n is an integer from 1 to 4, preferably from 1 to 2,

provided that when X is a hydrogen atom the n is 1.

U.S. Pat. No. 4,288,391, to Spivack, patented Sept. 8, 1981, providesalkylated 1,1'-biphenyl-2,2'-diylphosphites represented by the formula##STR31## wherein R is an alkyl group of 1 to 18 carbon atoms,

R₁ is hydrogen or an alkyl group of 1 to 18 carbon atoms, and

R₂ is an alkyl group of 1 to 20 carbon atoms, phenyl, phenyl substitutedby 1 to 3 alkyl groups each having 1 to 8 carbon atoms or by two alkylgroups each having 1 to 8 carbon atoms and by --COOR₄ where R₄ is alkylof 1 to 18 carbon atoms,

R₃ is an n-valent radical selected from the group consisting of astraight- or branched-chain alkylene of 2 to 12 carbon atoms, astraight- or branched-chain alkane-triyl, -tetrayl, -pentayl or -hexaylof 3 to 6 carbon atoms, alkenylene of 4 to 6 carbon atoms, cycloalkyleneof 6 to 12 carbon atoms, 1,4-cyclohexanedimethylene, arylene orarenetriyl of 6 to 10 carbon atoms, p-xylylene, phenylene--E--phenylenewhere E is a direct bond, --O--, --S--, --NR₅ --, where R₅ is alkyl of 1to 18 carbon atoms; a straight- or branched-chain alkylene or alkylideneof 1 to 12 carbon atoms or cycloalkylidene of 5 to 6 carbon atoms, saidarylene or said phenylene--E--phenylene substituted by 1 to 4 alkylgroups each having 1 to 8 carbon atoms, --(CH₂)_(x) S(CH₂)_(x) -- wherex is 2 to 6, dipentaerythrityl, and ##STR32## where Y is hydrogen,methyl or ethyl and z is 1 to 10, X is oxygen or sulfur, and

n is 2 to 6.

U.S. Pat. No. 4,318,845 to Spivack et al, patented Mar. 9, 1982,provides alkanolamine esters of 1,1'-biphenyl-2,2'-diyl-andalkylidene-1,1'-biphenyl-2,2'-diyl-cyclic phosphites corresponding tothe formula: ##STR33## such that when m=1, n=1 and p=1, m=2, n=1 andp=0, m=3, n and p are zero, and wherein

R is an alkyl group of 1 to 18 carbon atoms,

R₁ is hydrogen or an alkyl group of 1 to 18 carbon atoms;

R₂ is a direct bond or lower alkylene of 1 to 12 carbon atoms;

A is alkylene of 1 to 6 carbon atoms or cycloalkylene of 5 to 6 carbonatoms;

R₃ is an alkyl of 1 to 18 carbon atoms, or ##STR34## wherein Y is##STR35## A' is alkylene of 1 to 6 carbon atoms or cycloalkylene of 5 to6 carbon atoms,

m' is 1 or 2,

p is 0 or 1, and

q is 0-5

with A, R, R₁, R₂ being as previously defined; provided that when p andq are 0, --N--A'--N can be a diazacyloalkyl group of 2 to 10 carbonatoms or,

when m is 1 and p is 0, N--R₃ is an azacycloalkyl group of 2 to 10carbon atoms or an azaoxacycloalkyl group of 3 to 7 carbon atoms; and

R₄ is alkyl of 1 to 18 carbon atoms.

U.S. Pat. No. 4,362,830 to Minagawa et al, patented Dec. 7, 1982,provides hindered bis-phenol phenyl phosphites having the structure:##STR36## wherein: R is selected from the group consisting of alkylhaving from one up to about eighteen carbon atoms; cycloalkyl havingfrom three up to about twelve carbon atoms; alkaryl and aryl having fromsix to about eighteen carbon atoms; preferably, a bulky group such asiso, secondary or tertiary alkyl having from three to about ten carbonatoms; or cycloalkyl having six to twelve carbon atoms;

R₁ and R₂ are each selected from the group consisting of hydrogen; alkylhaving from one to about eighteen carbon atoms; cycloalkyl having fromthree up to about twelve carbon atoms; alkaryl and aryl having from sixto about eighteen carbon atoms; and are preferably in a position orthoto a phenolic hydroxyl or phenoxy group, if available;

R₃ is alkylene having from one to about six carbon atoms;

R₄ is selected from the group consisting of alkylene, cycloalkylene, andaralkylene, the residue of a monohydric or polyhydric alcohol, havingfrom one to about eighteen carbon atoms, and from none to three hydroxylgroups (originally one to four hydroxyl groups);

Y is selected from the group consisting of a direct carbon to carbonbond; thio sulfur --S--; oxy oxygen --O--; alkylidene having from one toabout six carbon atoms; and cycloalkylidene having from four to abouteight carbon atoms; and

n is 1, 2, 3, or 4, according to the valence of R₄.

U.S. Pat. No. 4,371,646 to Minagawa et al, patented Feb. 1, 1983,provides 2,6-di-tertiary butyl phenyl phosphites having the structure##STR37## wherein: R₁ is selected from the group consisting of hydrogen,methyl, ethyl, and (CH₂)_(m) COOR, where R is selected from the groupconsisting of alkyl having from one up to about ten carbon atoms;cyclaolkyl having from three up to about twelve carbon atoms; alkaryland aryl having from six to about twelve carbon atoms; and m is a numberwithin the range from 0 to 5;

R₂ is selected from the group consisting of hydrogen, alkyl having fromone to about twenty-two carbon atoms; cycloalkyl having from three up toabout twelve carbon atoms; alkaryl and aryl having from six to abouteighteen carbon atoms; the residue of a polyhydric alcohol having fromtwo to about eighteen carbon atoms, and from two to three hydroxylgroups; and the residue of a polyphenol having from six to abouteighteen carbon atoms and from two to about ten phenolic hydroxylgroups;

R₃ is selected from the group consisting of hydrogen and P(OR₂)₂ ;

Z is the bivalent to tetravalent residue of a polyhydric alcohol havingfrom two to about eighteen carbon atoms, and from two to five hydroxylgroups; or of a polyphenol having from six to about eighteen carbonatoms and from two to about ten phenolic hydroxyl groups;

n₁ is 0 or 1; and

n₂ is a number from 1 to 5.

U.S. Pat. No. 4,371,647 to Minagawa et al, patented Feb. 1, 1983,provides 2,6-di-tertiary butyl phenyl pentaerythritol spirobis-phosphites having the structure: ##STR38## wherein: R is alkylhaving from one to six carbon atoms;

R₁ is methyl or ethyl;

R₂ is selected from the group consisting of alkyl having from one up toabout eighteen carbon atoms; cycloalkyl having from three up to abouttwelve carbon atoms; and alkaryl and aryl having from six to aboutthirty carbon atoms; such groups substituted with from one to about fouroxy ether --O-- and/or carboxylic ester --COO-- groups ; the residue ofa polyhydric alcohol having from two to about eighteen carbon atoms, andfrom two to about ten hydroxyl groups; and the residue of a polyphenolhaving from six to about eighteen carbon atoms and from two to about tenphenolic hydroxyl groups.

In accordance with the present invention, alkylidene bisphenolphosphites and phosphates having 2,2,6,6-tetramethyl piperidinyl groupsare provided having the formula: ##STR39## wherein: R₁ is alkyl havingfrom one to about twelve carbon atoms;

R₂, R₃ R₄ are each selected from the group consisting of hydrogen andalkyl having from one to about twelve carbon atoms;

m is 0 or 1;

n is 0 or 1;

X is selected from the group consisting of ##STR40## wherein: R₅ isselected from the group consisting of hydrogen, oxyl O, alkyl havingfrom one to about twelve carbon atoms; aryl alkyl having from seven toabout eighteen carbon atoms; 2,3-epoxypropyl, acyl having from one toabout eight carbon atoms and ##STR41## in which R₆ is selected from thegroup consisting of hydrogen, alkyl having from one to about twelvecarbon atoms and phenyl, and Y₁ is selected from the group consisting ofhydrogen; acyl having from one to about twelve carbon atoms; and##STR42## Z₁ is selected from the group consisting of ##STR43## whereinR₇ is alkyl having from one to about twelve carbon atoms; and ##STR44##wherein: R₆ is selected from the group consisting of hydrogen, alkylhaving from one to about twelve carbon atoms and phenyl; and

Z₂ is selected from the group consisting of ##STR45## in which R₇ isalkyl having from one to about twelve carbon atoms; R₆ is alkylenehaving from one to about eight carbon atoms and Y₂ is selected from thegroup consisting of hydrogen and acyl having from one to about eightcarbon atoms.

It will be seen that according to the selection of X, Z₁ and Z₂ thefollowing subgenera fall within formula I: ##STR46##

Exemplary R₁, R₂, R₃, R₄, R₅, R₆ and R₇ alkyl include methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, amyl,isoamyl, tert-amyl, hexyl, isohexyl, tert-hexyl, heptyl, isoheptyl,isooctyl, octyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, sec-nonyl,tert-nonyl, decyl, isodecyl, tert-decyl, undecyl, isoundecyl, anddodecyl;

Exemplary R₅ arylalkyl include benzyl, phenylethyl, phenylpropyl,phenylbutyl, phenylamyl, phenylhexyl, phenyloctyl, phenylnonyl, andphenyldodecyl;

Exemplary R₆ alkylene include ethylene, 1,2-propylene, 1,3-propylene,2,2-dimethyl-1,3-propylene, 1,2-butylene and 1,2-ocytylene;

Exemplary R₅, Y₁ and Y₂ acyl include formyl, acetyl, propionyl,butyroyl, valeryl, hexanoyl, heptanoyl, octanoyl, acryloyl, methacryloyland benzoyl.

Typical compounds falling within the invention as represented by theformula (I) are: ##STR47##

These compounds can be readily prepared by reacting the correspondingbisphenol chlorophosphite or chlorophosphate of the formula ##STR48##with the piperidyl compound X--OH.

The following Examples are illustrative:

EXAMPLE I

Preparation of ##STR49## from the bisphenol chlorophosphite of theformula: ##STR50##

The bisphenol chlorophosphite, 2.5 g, 2,2,6,6-tetramethyl-4-piperidinol1.6 g, triethylamine 0.5 g and dichloroethane 25 ml were heated andstirred at 80° to 84° C. for ten hours under a stream of nitrogen gas.The precipitated triethylamine hydrochloride was filtered off, and thenthe solvent was stripped off. Benzene 50 ml was added, and the mixturewashed with water and dried. The benzene was distilled off, and 2.5 g ofwhite solid was obtained, M.P.=108°-113° C., I.R.: 840 cm⁻¹ (based onP--O--phenyl), 1010 cm⁻¹ : (based on P--O--alkyl).

EXAMPLE II

Preparation of ##STR51##

The bisphenol chlorophosphite of Example I, 2.5 g,9-aza-8,8,10,10-tetramethyl-3-ethyl-3-hydroxymethyl-1,5-dioxaspiro (5.5)undecane, 2.8 g triethylamine 0.5 g and dichloroethane 25 ml were heatedand stirred at 80° l to 84° C. for ten hours under a stream of nitrogengas. The precipitated triethylamine hydrochloride was filtered off, andthen the solvent was stripped off. Benzene 50 ml was added, and themixture washed with water and dried. The benzene was distilled off, and2.8 g of product, M.P. 102°-104.5° C. was obtained. I.R.: 830 cm⁻¹(based on P--O--phenyl), 1020 cm⁻¹ (based on P--O--alkyl), 1100 cm⁻¹(based on C--O--C).

EXAMPLE III

Preparation of ##STR52## from bisphenol chlorophosphate of the formula:##STR53##

The bisphenol chlorophosphate, 3.0 g, 2,2,6,6-tetramethyl-4-piperidinol1.8 g, triethylamine 0.6 g and dichloroethane 25 ml were heated andstirred at 80° to 84° C. for 15 hours under a stream of nitrogen gas.The precipitated triethylamine hydrochloride was filtered off, and thenthe solvent was stripped off. Benzene 50 ml was added, and the mixturewas washed with water and dried. The benzene was distilled off, and aglassy solid product, M.P. 93°-97° C., was obtained. I.R.: 945 cm¹(based on P--O--phenyl), 1020 cm¹ (based on P--O--alkyl).

Small amounts of the stablizer of this invention when combined withsynthetic resin improve the heat stability of the resin. The amount ofthe stablizer is generally within the range from about 0.001 to about 5parts by weight, preferably from about 0.01 to about 3 parts by weight,per 100 parts by weight of resin.

Synthetic resins that can have their resistance to deteriorationenhanced with the polymeric-stablizer compound according to thisinvention include α-olefin polymers such as polyethylene, polypropylene,polybutene, poly-3-methylbutene, or mixtures thereof and with copolymersother monomers such as ethylene-vinyl acetate copolymer;ethylene-propylene copolymer; polystyrene; polyvinyl acetate;polyacrylic esters; copolymers from styrene and another monomer (forexample, maleic anhydride, butadine, and acrylonitrile);acrylonitrile-butadienestyrene copolymer, acrylic acidester-butadiene-styrene copolymer, methacrylic acidester-butadine-styrene copolymer, polymethacrylate esters such aspolymethacrylate, polyvinyl alcohol; polyvinyl formal; polyvinylbutyral; linear polyesters, polyamides; polycarbonates; polyacetals;polyurethanes; cellulosic resins; phenol-formaldehyde resins;urea-formaldehyde resins; melamine-formaldehyde resins; epoxy resins;unsaturated polyester resins; silicone resins; halogen-containing resinssuch as polyvinyl chloride, polyvinylidene chloride, polyvinylidenefluoride, and copolymers thereof, and rubbers such as isoprene rubber,butadiene rubber, epichlorohydrin rubber, chloroprene rubber, and blendsof any of the above.

The alkylidene bisphenol phosphite and phosphate stabilizers of theinvention can be combined with conventional heat stablizers such asphenolic antioxidants, polyvalent metal salts of organic acids, organicphosphites, thioethers, and other known heat stabilizers, therebyconstituting heat and light stabilizer compositions of the invention.

The phenolic antioxidant contains one or more phenolic hydroxyl groups,and one or more phenolic nuclei, and can contain from about eight toabout three hundred carbon atoms. In addition, the phenolic nucleus cancontain an oxy or thio ether group.

The alkyl-substituted phenols and polynuclear phenols, because of theirmolecular weight, have a higher boiling point, and therefore arepreferred because of their lower volatility. There can be one or aplurality of alkyl groups of one or more carbon atoms. The alkyl groupor groups including any alkylene groups between phenol nuclei preferablyaggregate at least four carbon atoms. The longer the alkyl or alkylenechain, the better the compatibility with polypropylene, inasmuch as thephenolic compound then acquires more of an aliphatic hydrocarboncharacter, and therefore there is no upper limit on the number of alkylcarbon atoms. Usually, from the standpoint of availability, the compoundwill not have more than about eighteen carbon atoms in an alkyl,alicyclidene and alkylene group, and a total of not over about fiftycarbon atoms. The compounds may have from one to four alkyl radicals perphenol nucleus.

The phenol contains at least one and preferably at least two phenolichydroxyls, the two or more hydroxyls being in the same ring, if there isonly one. In the case of bicyclic phenols, the rings can be linked bythio or oxyether groups, or by alkylene, alicyclidene or arylidenegroups.

The monocyclic phenols which can be employed have the structure:##STR54## R is selected from the group consisting of hydrogen; halogen;and organic radicals containing from one to about thirty carbon atoms,such as alkyl, aryl, alkenyl, alkaryl, aralkyl, cycloalkenyl,cycloalkyl, alkoxy, and acyl ##STR55## where R' is aryl, alkyl orcycloalkyl.

x₁ and x₂ are integers from one to four, and the sum of x₁ and x₂ doesnot exceed six.

The polycyclic phenol phenol is one having at least two aromatic nucleilinked by a polyvalent linking radical, as defined by the formula:##STR56## wherein Y is a polyvalent linking group selected from thegroup consisting of oxygen; carbonyl; sulfur; sulfinyl; aromatic,aliphatic and cycloaliphatic hydrocarbon groups; and oxyhydrocarbon,thiohydrocarbon and heterocyclic groups. The linking group can have fromone up to twenty carbon atoms.

Ar is a phenolic nucleus which can be a phenyl or a polycarbocyclicgroup having condensed or separate phenyl rings; each Ar group containsat least one free phenolic hydroxyl group up to a total of five. The Arrings can also include additional rings connected by additional linkingnuclei of the type Y, for example, Ar--Y--Ar--Y--Ar.

m₁ and m₂ are numbers from one to five, and n₁ and n₂ are numbers of oneor greater, and preferably from one to four.

The aromatic nucleus Ar can, in addition to phenolic hydroxyl groups,include one or more inert substituents. Examples of such inertsubstituents include hydrogen, halogen atoms, e.g., chlorine, bromineand fluorine; organic radicals containing from one to about thirtycarbon atoms, such as alkyl, aryl, alkaryl, aralkyl, cycloalkenyl,cycloalkyl, alkoxy, aryloxy and acyloxy ##STR57## R' is aryl, alkyl orcycloalkyl, or thiohydrocarbon groups having from one to about thirtycarbon atoms, and carboxyl ##STR58## groups. Usually, however, eacharomatic nucleus will not have more than about eighteen carbon atoms inany hydrocarbon substituent group. The Ar group can have from one tofour substituent groups per nucleus.

Typical aromatic nuclei include phenyl, naphthyl, phenanthryl,triphenylenyl, anthracenyl, pyrenyl, chrysenyl, and fluoroenyl groups.

When Ar is a benzene nucleus, the polyhydyric polycyclic phenol has thestructure: ##STR59## wherein R₁, R₂ and R₃ are inert substituent groupsas described in the previous paragraph;

m₁ and m₃ are integers from one to a maximum of five;

m₂ is an integer from one to a maximum of four;

x₁ and x₃ are integers from zero to four, and

x₂ is an integer from zero to three;

y₁ is an integer from zero to about six and

y₂ is an integer from one to five, preferably one or two.

Preferably, the hydroxyl groups are located ortho and/or para to Y.

Exemplary Y groups are alkylene, alkylidene, and alkenylene; arylene,alkyl arylene, arylalkylene; cycloalkylene, cycloalkylidene; and oxa-and thia-substituted such groups; tetrahydrofuranes, esters and triazinegroups. The Y groups are usually bi, tri, or tetravalent, connectingtwo, three or four Ar groups. However, higher valency Y groupsconnecting more than four Ar groups, can also be used. According totheir constitution, the Y groups can be assigned to subgenera asfollows:

(1) Y groups where at least one carbon in a chain or cyclic arrangementconnect the aromatic groups, such as: ##STR60##

(2) Y groups where only atoms other than carbon link the aromatic rings,such as ##STR61## where x is a number from one to ten;

(3) Y groups made up of more than a single atom including both carbonand other atoms linking the aromatic nuclei, such as: ##STR62##

Although the relation of effectiveness to chemical structure isinsufficiently understood, many of the most effective phenols have Ygroups of subgenus (1), and accordingly this is preferred. Some of thesephenols can be prepared by the alkylation of phenols or alkyl phenolswith polyunsaturated hydrocarbons such as dicyclopentadiene orbutadiene.

Representative phenols include guaiacol, resorcinol monoacetate,vanillin, butyl salicylate, 2,6-di-tert-butyl-4-methyl phenol,2-tert-butyl-4-methoxy phenol, 2,4-dinonyl phenol, 2,3,4,5-tetradecylphenol, tetrahydro-α-naphthol, o-, m- and p-cresol, o-, m- andp-phenylphenol, o-, m- and p-xylenols, the carvenols, symmetricalxylenol, thymol, o-, m- and p-nonylphenol, o-, m- and p-dodecyl-phenol,and o-, m- and p-octyl-phenol, o-, and m-tert-butyl-p-hydroxy-anisole,p-n-decyloxy-phenol, p-n-decyloxy-cresol, nonyl-n-decyloxy-cresol,eugenol, isoeugenol, glyceryl monosalicylate,methyl-p-hydroxy-cinnamate, 4-benzyloxy-phenol, p-acetylaminophenol,p-stearyl-aminophenol, methyl-p-hydroxybenzoate,p-di-chlorobenzoyl-aminophenol, p-hydroxysalicyl anilide,-stearyl-(3,5-di-methyl-4-hydroxy-benzyl)thioglycolate,stearyl-β-(4-hydroxy-3,5-di-t-butylphenyl) propionate,distearyl-3,5-di-t-butyl-4-hydroxybenzylphosphonate, and distearyl(4-hydroxy-3-methyl-5-t-butyl) benzylmalonate.

Exemplary polyhydric phenols are orcinol, propyl gallate, catechol,resorcinol, 4-octyl-resorcinol, 4-dodecylresorcinol,4-octadecyl-catechol, 4-isooctyl-phloroglucinol, pyrogallol,hexahydroxybenzene, 4-isohexylcatechol,2,6-di-tertiary-butyl-resorcinol, 2,6-di-isopropyl-phloroglucinol.

Exemplary polyhydric polycyclic phenols are methylenebis-(2,6-di-tertiary-butyl-phenol), 2,2-bis-(4-hydroxy phenyl)-propane,methylene-bis-(p-cresol), 4,4'-benzylidene bis(2-tertiary-butyl-5-methyl-phenol), 4,4'-cyclo-hexylidenebis-(2-tertiary-butylphenol),2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)-phenol),2,6-bis-(2'-hydroxy-3'-tertiarybutyl-5'-methylbenzyl)-4-methylphenol,4,4'-bis-(2-tertiary-butyl-5-methyl-phenol), 2,2'-bis-(4-hydroxy-phenyl)butane, ethylene bis-(p-cresol), 4,4'-oxobis-phenol,4,4'-oxobis-(3-methyl-5-isopropyl-phenol),4,4'-oxobis-(3-methyl-phenol), 2,2'-oxobis-(4-dodecyl-phenol),2,2'-oxobis-(4-methyl-5-tertiary-butyl-phenol), 4,4'-thio-bis-phenol;4,4'-thio-bis-(3-methyl-6-tertiary-butyl-phenol),2,2'-thio-bis-(4-methyl-6-tertiary-butyl-phenol),4,4'-n-butylidene-(2-t-butyl-5-methylphenol),2,2'-methylene-bis-(4-methyl-6-(1'-methyl-cyclohexyl)phenol),4,4'-cyclohexylene bis-(2-tertiary-butyl-phenol),2,6-bis-(2'-hydroxy-3'-t-butyl-5'-methyl-benzyl)-4-methylphenol,4,4'-oxobis (naphthalene-1,5-diol), 1,3'-bis-(naphthalene-2,5-diol)propane, and 2,2'-butylene bis-(naphthalene-2,7-diol),(3-methyl-5-tert-butyl-4-hydroxyphenyl)-4'-hydroxy-phenyl)propane,2,2'-methylene-bis-(4-methyl-5-isopropylphenol),2,2'-methylene-bis-(4-methyl-5-isopropylphenol),2,2'-methylene-bis-(5-tert-butyl-4-chlorophenol),(3,5-di-tert-butyl-4-hydroxyphenyl)-(4 'hydroxyphenyl)ethane,(2-hydroxy-phenyl)-(3',5'-di-tert-butyl-4',4-hydroxyphenyl) ethane,2,2'-methylene-bis-(4-octylphenol),4,4'-propylene-bis-(2-tert-butyl-phenol),2,2'-isobutylene-bis-(4-nonylphenol),2,4-bis-(4-hydroxy-3-t-butyl-phenoxy)-6-(n-octylthio)-1,3,5-triazine,2,4,6-tris-(4-hydroxy-3-t-butyl-phenoxy)-1,3,5-triazine, 2,2'-bis-(3-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)thiazole,2,2'-bis-(3-methyl-5-t-butyl-4-hydroxyphenyl)thiazolo-(5,4-d)-thiazole,4,4'-bis-(4-hydroxyphenyl)pentanoic acid octadecyl ester,cyclopentylene-4,4'-bis-phenol, 2-ethylbutylene-4,4'-bisphenol,4,4'-cyclooctylene-bis-(2-cyclohexylphenol),β,β-thiodiethanol-bis-(3-tert-butyl-4-hydroxyphenoxy acetate),1,4-butanedio-bis-(3-tert-butyl-4-hydroxyphenoxy acetate),pentaerythritol tetra-(4-hydroxyphenol propionate), 2,4,4'-tri-hydroxybenzophenone, bis-(2-tert-butyl-3-hydroxy-5-methylphenyl)sulfide,bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfide,bis-(2-tert-butyl-4-hydroxy-5-methylphenyl)sulfoxide,bis-(3-ethyl-5-tert-butyl-4-hydroxybenzyl)sulfide,bis-(2-hydroxy-4-methyl-6-tert-butyl-phenyl)sulfide,4,4'-bis-(4-hydroxyphenol)pentanoic acid octadecyl thiopropionate ester,1,1,3-tris-(2'-methyl-4-hydroxy-5'-tert-butylphenyl)butane,1,1,3-tris-(1-methyl-3-hydroxy-4-tert-butylphenyl)butane,1,8-bis-(2-hydroxy-5-methylbenzoyl-n-octane,2,2'-ethylene-bis-[4'-(3-tert-butyl-4-hydroxyphenyl)-thiazole],1-methyl-3-(3-methyl-5-tert-butyl-4-hydroxybenzyl)-naphthalene, 2,2'-(2-butene)-bis-(4-methoxy-6-tert-butylphenol)-bis-[3,3-bis-(4-hydroxy-3-t-butylphenyl)butyricacid]glycol ester, 4,4'-butylidene-bis-(6-t-butyl-m-cresol),1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane,1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane,1,3,5-tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethylisocyanurate,2-octylthio-4,6-di-(4-hydroxy-3,5-di-t-butyl)phenoxy-1,3,5-triazine,4,4'-thiobis-(6-t-butyl-m-cresol) and pentaerythritol hydroxyphenylpropionate.

A particularly desirable class of polyhydric polycyclic phenols are thedicyclopentadiene polyphenols, which are of the type: ##STR63## in whichR₁ and R₂ are lower alkyl, and can be the same or different, and

n is the number of the groups enclosed by the brackets,

and is usually from 1 to about 5. These are described in U.S. Pat. No.3,567,683, dated Mar. 2, 1971 to Spacht. A commercially available memberof this class is Wingstay L, exemplified by dicyclopentadienetri-(2-tert-butyl-4-methyl-phenol) of the formula: ##STR64##

The polyhydric polycyclic phenols used in the invention can also becondensation products of phenols or alkylphenols with hydrocarbonshaving a bicyclic ring structure and a double bond or two or more doublebonds, such as α-pinene, β-pinene, dipentene, limonene,vinylcyclohexene, dicyclopentadiene, allo-ocimene, isoprene andbutadiene. These condensation products are usually obtained under acidicconditions in the form of more or less complex mixtures of monomeric andpolymeric compounds. However, it is usually not necessary to isolate theindividual constituents. The entire reaction product, merely freed fromthe acidic condensation catalyst and unchanged starting material, can beused with excellent results. While the exact structure of these phenoliccondensation products is uncertain, the Y groups linking the phenolicnuclei all fall into the preferred subgenus 1. For method ofpreparation, see e.g., U.S. Pat. No. 3,124,555, U.S. Pat. No. 3,242,135,and British Pat. No. 961,504.

When the stabilizer composition is used in conjunction with a polyvalentmetal salt of an organic acid, the organic acid will ordinarily havefrom about six to about twenty-four carbon atoms. The polyvalent metalcan be any metal of Group II of the Periodic Table, such as zinc,calcium, cadmium, barium, magnesium and strontium. The alkali metalsalts and heavy metal salts such as lead salts are unsatisfactory. Theacid can be any organic non-nitrogenous monocarboxylic acid having fromsix to twenty-four carbon atoms. The aliphatic, aromatic, alicyclic andoxygen-containing heterocyclic organic acids are operable as a class. Bythe term "aliphatic acid" is meant any open chain carboxylic acid,substituted, if desired, with nonreactive groups, such as halogen,sulfur and hydroxyl. By the term "alicyclic" it will be understood thatthere is intended any cyclic acid in which the ring is nonaromatic andcomposed solely of carbon atoms, and such acids may if desired haveinert, nonreactive substituents such as halogen, hydroxyl, alkylradicals, alkenyl radicals and other carbocyclic ring structurescondensed therewith. The oxygen-containing heterocyclic compounds can bearomatic or nonaromatic and can include oxygen and carbon in the ringstructure, such as alkylsubstituted furoic acid. The aromatic acidslikewise can have nonreactive ring substituents such as halogen, alkyland alkenyl groups, and other saturated or aromatic rings condensedtherewith.

As exemplary of the acids which can be used in the form of their metalsalts there can be mentioned the following: hexoic acid, 2-ethylhexoicacid, n-octoic acid, iooctoic acid, capric acid, undecylic acid, lauricacid, myristic acid, palmitic acid, margaric acid, stearic acid, oleicacid, ricinoleic acid, behenic acid, chlorocaproic acid, hydroxy capricacid, benzoic acid, phenylacetic acid, butyl benzoic acid, ethyl benzoicacid, propyl benzoic acid, hexyl benzoic acid, salicylic acid, naphthoicacid, 1-naphthalene acetic acid, orthobenzoyl benzoic acid, naphthenicacids derived from petroleum, abietic acid, dihydroabietic acid,hexahydrobenzoic acid, and methyl furoic acid.

The water-insoluble salts are preferred, because they are not leachedout when the plastic is in contact with water. Where these salts are notknown, they are made by the usual types of reactions, such as by mixingthe acid, or anhydride with the corresponding oxide or hydroxide of themetal in a liquid solvent, and heating, if necessary, until saltformation is complete.

The thiodipropionic acid ester has the following formula:

    R.sub.1 OOCCH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 COOY

in which R₁ is an organic radical selected from the group consisting ofhydrocarbon radicals such as alkyl, alkenyl, aryl, cycloalkyl and mixedalkyl aryl and mixed alkyl cycloalkyl radicals; hydroxyalkyl andhydroxyalkyloxyalkylene radicals; and esters thereof with aliphaticcarboxylic acids; and Y is selected from the group consisting of (a)hydrogen, (b) a second R radical R₂, which can be the same as ordifferent from the R₁ radical, (c) a polymeric chain of nthiodipropionic acid ester units:

    --XO[OCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOXO].sub.n OCCH.sub.2 CH.sub.2 --S--CH.sub.2 CH.sub.2 COOZ

where Z is hydrogen, R₂ or M, n is the number of thiodipropionic acidester units in the chain, and X is a bivalent hydrocarbon group of thetype of R₁, that is, alkylene, alkenylene, cycloalkylene, mixedalkylene-arylene and mixed alkylene-cycloalkylene radicals;hydroxyalkylene and hydroxyalkyloxyalkylene radicals; and esters thereofwith aliphatic carboxylic acids; the value of n can range upwards from0, but there is no upper limit on n except as is governed by the ratioof carbon atoms to sulfur atoms as stated below; and (d) a polyvalentmetal M of Group II of the periodic table such as zinc, calcium,cadmium, barium, magnesium and strontium.

The molecular weights of the R and Y radicals are taken such that withthe remainder of the molecule the thiodipropionic ester has a total offrom about ten to about sixty carbon atoms per sulfur atom.

Accordingly, the various thiodipropionic acid ester species coming withthe above-designated catagories within the general formula can bedefined as follows:

    R.sub.1 OOCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOH       (a)

    R.sub.1 OOCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOR.sub.2 (b)

    R.sub.1 O[OCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOX--O].sub.n OCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOZ                          (c)

    R.sub.1 OOCCH.sub.2 CH.sub.2 SCH.sub.2 CH.sub.2 COOM       (d)

In the above formulae R₁ and R₂, M, X and Z are the same as before andthe value of n₁ can range upwards from 1, but there is no upper limit onn₁ except as is imposed by the ratio of carbon atoms, as stated below.In the polymer (c), as in the other forms of thiodipropionic acidesters, the total number of carbon atoms per sulfur atom is within therange from about ten to about sixty.

The R radical of these esters is important in furnishing compatibilitywith the polymer. The Y radical is desirably a different radical, R₂ orM or a polymer, where R is rather low in molecular weight, so as tocompensate for this in obtaining the optimum compatibility andnonvolatility. Where Y is a metal, the thiodipropionic acid esterfurnishes the beneficial properties of the polyvalent metal salt whichis described above.

The aryl, alkyl, alkenyl, and cycloalkyl groups may, if desired, containinert, nonreactive substituents, such as halogen and other carbocyclicand heterocyclic ring structures condensed therewith.

Typical R radicals are, for example, methyl, ethyl, propyl, isopropyl,butyl, isobutyl, t-butyl, amyl, isoamyl, n-octyl, isooctyl, 2-ethylhexyl, t-octyl, decyl, dodecyl, octadecyl, allyl, hexenyl, linoleyl,ricinoleyl, oleyl, phenyl, xylyl, tolyl, ethylphenyl, naphthyl,cyclohexyl, benzyl, cyclopentyl, methylcyclohexyl, ethylcyclohexyl, andnaphthenyl, hydroxyethyl, hydroxypropyl, glyceryl, sorbityl,pentaerythrityl, and polyoxyalkylene radicals such as those derived fromdiethylene glycol, triethylene glycol, polyoxypropylene glycol,polyoxyethylene glycol, and polyoxypropyleneoxyethylene glycol, andesters thereof with any of the organic acids named below in thediscussion of the polyvalent metal salts, including in addition thoseorganic acids having from two to five carbon atoms, such as acetic,propionic, butyric and valeric acids.

Typical X radicals are alkylene radicals such as ethylene,tetramethylene, hexamethylene, decamethylene, alkyl-substituted alkyleneradicals such as 1,2-propylene, ##STR65##

As exemplary of the thiodipropionic acid esters which can be used, therecan be mentioned the following: monolauryl thiodipropionic acid;dilauryl thiodipropionate, butyl stearyl thiodipropionate, 2-ethylhexyllauryl thiodipropionate, di-2-ethylhexyl-thiodipropionate, diisodecylthiodipropionate, isodecyl phenyl thiodipropionate, benzyl laurylthiodipropionate, benzyl phenyl thiodipropionate, the diester of mixedcoconut fatty alcohols and thiodipropionic acid, the diester of mixedtallow fatty alcohols and thiodipropionic acid, the acid ester of mixedcottonseed oil fatty alcohols and thiodipropionic acid, the acid esterof mixed soyabean oil fatty alcohols and thiodipropionic acid,cyclohexyl nonyl thiodipropionate, monooleyl thiodipropionic acid,hydroxyethyl lauryl thiodipropionate, monoglyceryl thiodipropionic acid,glyceryl monostearate monothiodipropionate, sorbityl isodecylthiodipropionate, the polyester of diethylene glycol and thiodipropionicacid, the polyester of triethylene glycol and thiodipropionic acid, thepolyester of hexamethylene glycol and thiodipropionic acid, thepolyester of pentaerythritol and thiodipropionic acid, the polyester ofoctamethylene glycol and thiodipropionic acid, the polyester ofp-dibenzyl alcohol and thiodipropionic acid, ethylbenzyl laurylthiodipropionate, strontium stearyl thiodipropionate, magnesium oleylthiodipropionate, calcium dodecylbenzyl thiodipropionate, andmono(dodecylbenzyl)thiodipropionic acid.

These esters are for the most part known compounds, but where they arenot available, they are readily prepared by esterification ofthiodipropionic acid and the corresponding alcohol.

Also useful are:

(1) Thioalkanoic acid amides of Tokuno et al Japanese Pat. No. 16,286/68having the formula: ##STR66## R is alkyl of one to eight carbon atoms,R₁ is alkyl of six to twenty-four carbon atoms, and R₂ is alkylene ofone to six carbon atoms.

(2) Thioalkanoic acid amides of 1,3,5-triazines of Ozeki et al JapanesePat. No. 20,366/68 having the formula: ##STR67## R is alkyl of eight toeighteen carbon atoms.

(3) Bis-thioalkanoic acid amides of Yamamoto et al Japanese Pat. No.23,765/68 having the formula: ##STR68## R is alkyl of more than sixcarbon atoms, aryl or aralkyl.

(4) Bis-thioalkylanoic acid amides of Ozeki et al Japanese Pat. No.26,184/69 having the formula: ##STR69## R is alkyl of twelve to eighteencarbon atoms, and R₁ is alkylene of one to ten carbon atoms,cycloalkylene, or arylene.

(5) Bis-alkylene thioalkanoic acid amides of Ozeki Japanese Pat. No.31,464/69 having the formula: ##STR70## R is alkyl of more than sixcarbon atoms, aryl, or aralkyl.

(6) Thioalkanoic acid amide derivatives of Minagawa et al, publishedJapanese application No. 106,484/74 having the formula: ##STR71## R ishydrocarbyl of one to twenty carbon atoms.

(7) Alkylene bis-thioalkanoic acid amides of U.S. Pat. No. 4,279,805 toOhzeki et al, patented July 21, 1981, having the general formula:##STR72## wherein: R₁ is alkyl having from one to about fifty carbonatoms;

R₂ is alkylene having from one to about three carbon atoms; and

R₃ is alkylene having from about two to about twelve carbon atoms.

β-Alkylthiopropionic acid esters having the general formula:

    R--S--C.sub.2 H.sub.4 COOR--R').sub.n

wherein:

R is alkyl of four to twenty carbon atoms;

n is a number from 1 to 6; and

R' is the residue of an alcohol having from one to six hydroxyl groups.

Pentaerythritol tetra dodecyl thio propionate is an example of thisgroup.

In addition, the usual light stabilizers can be employed, such as2,2,6,6-tetramethyl piperidyl compounds, hydroxybenzophenones such as2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxy benzophenone,2,4-dihydroxybenzophenone, benzotriazoles, such as2(2-hydroxy-5-methylphenyl)benzotriazoles,2(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole,2(2-hydroxy-3-5-di-t-butylphenyl)5-chlorobenzotriazole,2(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole, benzoates such asphenylsalicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxyphenylbenzoate, nickel compounds such asnickel-2,2-'-thiobis(4-t-octyl-phenolate),nickel-monoethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, substitutedacrylonitriles such as methyl-α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate and oxalic anilides such as N-2-ethylphenyl-N'-2-ethoxy-5-t-butyl phenyl oxalic diamide, N-2-ethylphenyl-N'-2-ethoxy phenyl oxalic diamide.

A sufficient amount of the stabilizer or combination is used to improvethe resistance of the synthetic polymer to deterioration in physicalproperties when exposed to heat and light, including, for example,discoloration, reduction in melt viscocity and embrittlement. Very smallamount are usually adequate. Amounts within the range from about 0.001to about 10% total stabilizers including the heat and light stabilizerof the invention by weight of the polymer are satisfactory. Preferably,from 0.01 to 5% is employed for optimum stabilization.

When all components are solids, the stabilizer systems of the inventionare readily rendered in solid particulate form, comprising a blend of:

(a) alkylidene bisphenol phosphite and phosphate in an amount of fromabout 10 to about 35 parts by weight;

and optionally:

(b) a phenolic antioxidant in an amount from about 10 to about 35 partsby weight; and/or

(c) other heat or light stabilizers in an amount of from about 10 toabout 35 parts by weight.

The alkylidene bisphenol phosphite and phosphate of the invention can beemployed in combination with phenolic antioxidant and/or otherconventional heat and light stabilizers for the particular syntheticpolymer.

Thus, for example, in the case of polyvinyl chloride resins, otherpolyvinyl chloride resin heat stabilizers can be included, includingpolyvalent metal fatty acid salts such as barium and cadmium salts ofthe higher fatty acids; organotin compounds; and epoxy compounds.

With polyolefin resins there can be employed fatty acid salts ofpolyvalent metals, and the higher fatty acid esters of thiodipropionicacids, such as, for example, dilauryl thiodipropionate.

With polyamide resin compositions, polyamide stabilizers such as coppersalts in combination with iodides and/or other phosphorus compounds andsalts of divalent manganese can be used.

With synthetic rubbers and acrylonitrile-butadiene-styrene terpolymers,other antioxidants and polyvalent metal salts of the higher fatty acidscan be used.

In addition, other conventional additives for synthetic polymers, suchas plasticizers, lubricants, emulsifiers, antistatic agents,flame-proofing agents, pigments and fillers, can be employed.

The stabilizer or combination is incorporated in the polymer in suitablemixing equipment, such as a mill or a Banbury mixer. If the polymer hasa melt viscosity which is too high for the desired use, the polymer canbe worked until its melt viscosity has been reduced to the desired rangebefore addition of the stabilizer. Mixing is continued until the mixtureis substantially uniform. The resulting composition is then removed fromthe mixing equipment and brought to the size and shape desired formarketing or use.

The stabilized polymer can be worked into the desired shape, such as bymilling, calendering, extruding or injection molding or fiber-forming.In such operations, it will be found to have a considerably improvedresistance to reduction in melt viscosity during the heating, as well asa better resistance to discoloration and embrittlement on ageing andheating.

The following Examples illustrate preferred stabilizer systems and resincompositions of the invention:

EXAMPLES 1 TO 6

Polypropylene compositions were prepared using stabilizers of thisinvention and two of the prior art, and having the followingformulation:

    ______________________________________                                        Ingredient           Parts by Weight                                          ______________________________________                                        Unstabilized polypropylene                                                                         100                                                      Calcium stearate     0.2                                                      Pentaerythritol tetrakis(3,5-di-t-                                                                 0.1                                                      butyl-4-hydroxyphenylpropionate)                                              Stabilizer as shown in Table I                                                                     0.2                                                      ______________________________________                                    

The compositions were thoroughly blended in a Brabender Plastograph, andthen compression-molded to form sheets 0.3 mm thick. Pieces 2.5 cm² werecut off from the sheets and exposed to a high voltage mercury lamp. Thehours to failure were noted.

The compositions were each extruded at 300° C. for five times, and themelt flow index (MFI) (at 230° C., load: 2160 g) was measured. The ratioof MFI (MFI after extruded five times (MFI-5)/MFI after extruded onetime (MFI-1) was also determined. The results are shown in Table I.

                                      TABLE I                                     __________________________________________________________________________                                                        Hours                                                                               MFI-5/              Example No.                                                                          Stabilizer                                   Failure                                                                            MFI-1                __________________________________________________________________________    Control 1                                                                            None                                         120  4.1                  Control 2                                                                             ##STR73##                                   250  3.5                  Control 3                                                                             ##STR74##                                   220  3.2                  Example 1                                                                             ##STR75##                                   370  1.9                  Example 2                                                                             ##STR76##                                   350  1.8                  Example 3                                                                             ##STR77##                                   350  1.8                  Example 4                                                                             ##STR78##                                   330  2.1                  Example 5                                                                             ##STR79##                                   300  2.4                  Example 6                                                                             ##STR80##                                   300  2.0                  __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

EXAMPLES 7 TO 12

High density polyethylene compositions were prepared using stabilizersof the invention and two of the prior art, and having the followingformulation:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        High-density polyethylene                                                                         100                                                       Calcium stearate    1.0                                                       Stearyl-3,5-di-t-butyl-4-                                                                         0.1                                                       hydroxyphenylpropionate                                                       Stabilizer as shown in Table II                                                                   0.2                                                       ______________________________________                                    

The stabilizer was blended with the polymer on a two-roll mill andsheets 0.5 mm thick were prepared by compression-molding of the blend.Pieces 2.5 cm square were cut off from the sheets, and exposed in aWeather-O-Meter to ultraviolet light, and heated at 150° C. in a Geeroven on aluminum foil. The time in hours when degradation set in, asdetermined by a significant discoloration and/or embrittlement, wasnoted as hours to failure. The results are shown in Table II.

                                      TABLE II                                    __________________________________________________________________________                                                           Hours to Failure       Example                                                Geer                                                                             Weather-            No.   Stabilizer                                       oven                                                                             O-Meter             __________________________________________________________________________    Control 1                                                                            ##STR81##                                       680                                                                              460                 Control 2                                                                            ##STR82##                                       620                                                                              510                 Example 7                                                                            ##STR83##                                       930                                                                              680                 Example 8                                                                            ##STR84##                                       900                                                                              660                 Example 9                                                                            ##STR85##                                       930                                                                              700                 Example 10                                                                           ##STR86##                                       860                                                                              650                 Example 11                                                                           ##STR87##                                       840                                                                              600                 Example 12                                                                           ##STR88##                                       800                                                                              650                 __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

EXAMPLES 13 TO 18

A group of polyvinyl chloride resin compositions was prepared having thefollowing formulation:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Polyvinyl chloride  100                                                       Di-2-ethylhexylphthalate                                                                          45                                                        Tricresylphosphate  5                                                         Bisphenol A.diglycidylether                                                                       3                                                         Zinc stearate       0.6                                                       Barium stearate     0.3                                                       Barium nonylphenolate                                                                             0.3                                                       Sorbitan monopalmitate                                                                            2.0                                                       Methylenebis(stearamide)                                                                          0.3                                                       Stabilizer as shown in Table III                                                                  0.3                                                       ______________________________________                                    

This formulation was blended and sheeted off on a two-roll mill to formsheets 0.1 mm thick.

The sheets were heated in air in a Geer oven at 190° C. to evaluate heatstability, and the time in minutes noted for the sheet to develop anoticeable discoloration and/or embrittlement.

The light stability of these sheets was determined by placing the sheetsin a Weather-O-Meter, and exposing them to ultraviolet light. The timein hous was then noted for the sheets to develop a noticeablediscoloration and/or embrittlement. The results are shown in Table III.

                                      TABLE III                                   __________________________________________________________________________                                              Heat Stability                                                                       Light Stability              Example No.                                                                          Stabilizer                         (minutes)                                                                            (hours)                      __________________________________________________________________________    Control 1                                                                            Octyl diphenyl phosphite           100    1200                         Control 2                                                                             ##STR89##                         105    2200                         Control 3                                                                             ##STR90##                         110    2500                         Example 13                                                                            ##STR91##                         130    4400                         Example 14                                                                            ##STR92##                         120    3600                         Example 15                                                                            ##STR93##                         135    4200                         Example 16                                                                            ##STR94##                         125    3500                         Example 17                                                                            ##STR95##                         130    4200                         Example 18                                                                            ##STR96##                         120    3500                         __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

EXAMPLES 19 TO 24

Acrylonitrile-butadiene-styrene terpolymer resin compositions wereprepared using stabilizers of the invention and two of the prior art,and having the following formulation:

    ______________________________________                                        Ingredient          Parts by Weight                                           ______________________________________                                        Acrylonitrile-butadiene-styrene                                                                   100                                                       terpolymer                                                                    4,4'-Butylidene-bis(2-t-butyl-                                                                    0.1                                                       m-cresol)                                                                     Stabilizer as shown in Table IV                                                                   0.3                                                       ______________________________________                                    

The stabilizer was blended with the resin on a two-roll mill, and sheets3 mm thick were prepared by compression molding of the resulting blend.

Pieces 2.5 cm square were cut off from the sheets, and exposed toultraviolet light in a Weather-O-Meter for 800 hours. Tensile strengthbefore and after the exposure was determined, and the results reportedas the percent of tensile strength retained, at the end of this time, inTable IV. Heat stability was evaluated by heating the specimen sheets at210° C. for ten minutes. The color of the specimens was noted and gradedon a scale from 1 to 10, in which 1 shows white and 10 shows brown. Theresults are shown in Table IV.

                                      TABLE IV                                    __________________________________________________________________________                                                         %                                                                             Retention                                                                           Color                                                                   of                                                                                  ofnsile            Example No.                                                                          Stabilizer                                    Strength                                                                            Sheets             __________________________________________________________________________    Control 1                                                                             ##STR97##                                    50    5                  Control 2                                                                             ##STR98##                                    48    6                  Example 19                                                                            ##STR99##                                    74    2                  Example 20                                                                            ##STR100##                                   75    2                  Example 21                                                                            ##STR101##                                   75    2                  Example 22                                                                            ##STR102##                                   72    3                  Example 23                                                                            ##STR103##                                   73    4                  Example 24                                                                            ##STR104##                                   70    2                  __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

EXAMPLES 25 TO 30

Polyurethane resin compositions were prepared using stabilizers of theinvention and two of the prior art, and having the followingformulation:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Polyurethane resin (Asahi Denka U-100).sup.1                                                        100                                                     Barium stearate       0.7                                                     Zinc stearate         0.3                                                     Stabilizer as shown in Table V                                                                      0.3                                                     ______________________________________                                         .sup.1 A polyurethaneisocyanate made from toluene diisocyanate and            alkylene polyol.                                                         

The stabilizer was blended with the finely powdered polyurethane resinon a two-roll mill for five minutes at 70° C., and the sheet was thencompression-molded at 120° C. for five minutes to form sheets 0.5 mmthick. Pieces 2.5 cm square were cut off from the sheets, and exposed toultraviolet light in a Fade-O-Meter for fifty hours. Elongation beforeand after exposure was determined, and the percent elongation retainedafter the exposure is given in Table V.

                                      TABLE V                                     __________________________________________________________________________    Example                                                 % Retention           No.  Stabilizer                                         of                    __________________________________________________________________________                                                            Elongation            Control 1                                                                           ##STR105##                                        52                    Control 2                                                                           ##STR106##                                        48                    Example 25                                                                          ##STR107##                                        66                    Example  26                                                                         ##STR108##                                        65                    Example 27                                                                          ##STR109##                                        62                    Example 28                                                                          ##STR110##                                        62                    Example 29                                                                          ##STR111##                                        60                    Example 30                                                                          ##STR112##                                        63                    __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

EXAMPLES 31 TO 36

The stabilizers of this invention are effective as light stabilizers forcoatings.

The effect of the stabilizers in a two-coat metallic effect finishcomprising metallic effect priming lacquer and unpigmented finishinglacquer was determined.

(a) Metallic effect priming lacquer

An acrylic resin solution was prepared by heating and stirring a mixtureof methyl methacrylate 100 g, n-butylacrylate 66 g, 2-hydroxyethylmethacrylate 30 g, methacrylic acid 4 g, xylene 80 g and n-butanol 20 gat 110° C. while adding a solution of azobisisobutyronitrile 2 g,dodecylmercaptan 0.5 g, xylene 80 g and n-butanol 20 g dropwise overthree hours. The solution was then stirred an additional two hours at110° C.

The above acrylic resin solution 12 parts, butoxylated methylolmelamine(Mitsui-Toatsu Co., Yuban 20SE60; solids content 60%) 2.5 parts,cellulose acetobutyrate (20% butyl acetate solution) 50 parts, aluminumpigment (Toyo Aluminium Co., Alpaste 1123N) 5.5 parts, xylene 10 parts,butyl acetate 20 parts and copper phthalocyanine blue 0.2 part wereblended.

(b) Unpigmented finishing lacquer

The above acrylic resin solution 48 parts, butoxylated methylolmelamine10 parts, xylene 10 parts, butoxyethylacetate 4 parts and stabilizer asshown in Table VI 0.15 part were blended.

Pieces of steel sheeting, which were coated with a primer, were firstcoated with the priming lacquer and subsequently with the finishinglacquer. The printing lacquer was sprayed on to a thickness of about 20microns, and aired for 10 minutes. Then the clear lacquer was sprayed onto a thickness of about 30 microns. After being aired 15 minutes, thesamples were stoved for 30 minutes at 140° C.

The coated sheets were exposed to ultraviolet light in aWeather-O-Meter. The time in hours when degradation set in, asdetermined by cracking of a surface of the sheet, was noted as hours tofailure, and the results are shown in Table VI.

                                      TABLE VI                                    __________________________________________________________________________    Example No.                                                                          Stabilizer                         Hours to Failure                    __________________________________________________________________________    Control 1                                                                             ##STR113##                        2600                                Control 2                                                                             ##STR114##                        2800                                Example 31                                                                            ##STR115##                        4400                                Example 32                                                                            ##STR116##                        3700                                Example 33                                                                            ##STR117##                        4100                                Example 34                                                                            ##STR118##                        4000                                Example 35                                                                            ##STR119##                        3800                                Example 36                                                                            ##STR120##                        3800                                __________________________________________________________________________

The superiority of the bisphenol phosphites and phosphates of theinvention to the prior art compounds is apparent from the data.

Having regard to the foregoing disclosure the following is claimed asthe inventive and patentable embodiments thereof:
 1. Alkylidenebisphenol phosphites and phosphates having 2,2,6,6-tetramethylpiperidinyl groups having the formula: ##STR121## wherein: R₁ is alkylhaving from one to about twelve carbon atoms; R₂, R₃ and R₄ are eachselected from the group consisting of hydrogen and alkyl having from oneto about twelve carbon atoms;m is 0 or 1; n is 0 or 1; X is selectedfrom the group consisting of ##STR122## wherein: R₅ is selected from thegroup consisting of hydrogen, oxyl O, alkyl having from one to abouttwelve carbon atoms; aryl alkyl having from seven to about eighteencarbon atoms; 2,3-epoxypropyl, acyl having from one to about eightcarbon atoms and ##STR123## in which R₆ is selected from the groupconsisting of hydrogen, alkyl having from one to about twelve carbonatoms and phenyl, and Y₁ is selected from the group consisting ofhydrogen; acyl having from one to about twelve carbon atoms; and##STR124## Z₁ is selected from the group consisting of ##STR125##wherein R₇ is alkyl having from one to about twelve carbon atoms; and##STR126## wherein: R₆ is selected from the group consisting ofhydrogen, alkyl having from one to about twelve carbon atoms and phenyl;and Z₂ is selected from the group consisting of ##STR127## in which R₇is alkyl having from one to about twelve carbon atoms; R₈ is alkylenehaving from one to about eight carbon atoms and Y₂ is selected from thegroup consisting of hydrogen and acyl having from one to about eightcarbon atoms.
 2. Alkylidene bisphenol phosphites or phosphates accordingto claim 1 in which R₁ and R₂ are iso, secondary or tertiary alkylhaving from three to about ten carbon atoms.
 3. Alkylidene bisphenolphosphites or phosphates according to claim 1 in which R₂ is in a paraposition to the phenolic hydroxyl group.
 4. Alkylidene bisphenolphosphites or phosphates according to claim 1 in which n is
 0. 5.Alkylidene bisphenol phosphites or phosphates according to claim 1 inwhich n is
 1. 6. Alkylidene bisphenol phosphites or phosphates accordingto claim 1 in which n is 0 and m is
 0. 7. Alkylidene bisphenolphosphites or phosphates according to claim 1 in which n is 0 and mis
 1. 8. Alkylidene bisphenol phosphites or phosphates according toclaim 1 in which n is 1 and m is
 0. 9. Alkylidene bisphenol phosphitesor phosphates according to claim 1 in which n is 1 and m is
 1. 10.Alkylidene bisphenol phosphites or phosphates according to claim 1 inwhich X is ##STR128##
 11. Alkylidene bisphenol phosphites or phosphatesaccording to claim 10 in which Z₁ is ##STR129##
 12. Alkylidene bisphenolphosphites or phosphates according to claim 10 in which Z₁ is ##STR130##13. Alkylidene bisphenol phosphites or phosphates according to claim 1in which X is ##STR131##
 14. Alkylidene bisphenol phosphites orphosphates according to claim 13 in which Z₂ is >C═O.
 15. Alkylidenebisphenol phosphites or phosphates according to claim 13 in which Z₂ is>CH--O--Y₂.
 16. Alkylidene bisphenol phosphites or phosphates accordingto claim 13 in which Z₂ is ##STR132##
 17. Alkylidene bisphenolphosphites or phosphates according to claim 13 in which Z₂ is ##STR133##18. Alkylidene bisphenol phosphites or phosphates according to claim 1having the formula: ##STR134##
 19. Alkylidene bisphenol phosphites orphosphates according to claim 1 having the formula: ##STR135## 20.Alkylidene bisphenol phosphites or phosphates according to claim 1having the formula: ##STR136##
 21. Alkylidene bisphenol phosphites orphosphates according to claim 1 having the formula: ##STR137## 22.Alkylidene bisphenol phosphites or phosphates according to claim 1having the formula: ##STR138##
 23. Alkylidene bisphenol phosphites orphosphates according to claim 1 having the formula: ##STR139## 24.Alkylidene bisphenol phosphites or phosphates according to claim 1having the formula: ##STR140##
 25. Alkylidene bisphenol phosphites orphosphates according to claim 1 having the formula: ##STR141##
 26. Apolyvinyl chloride resin composition having improved resistance todeterioration to light comprising a polyvinyl chloride resin formed atleast in part of the recurring group ##STR142## and having a chlorinecontent in excess of 40%, where X is either hydrogen or chlorine; and analkylidene bisphenol phosphite or phosphate in accordance with claim 1.27. A polyvinyl chloride resin composition in accordance with claim 26,in which the polyvinyl chloride resin is polyvinyl chloride homopolymer.28. A polyvinyl chloride resin composition in accordance with claim 26,in which the polyvinyl chloride resin is a copolymer of vinyl chlorideand vinyl acetate.
 29. An olefin polymer composition having improvedresistance to deterioration when exposed to light comprising an olefinpolymer selected from the group consisting of alpha-olefins having fromtwo to six carbon atoms and polystyrene, and an alkylidene bisphenolphosphite or phosphate in accordance with claim
 1. 30. An olefin polymercomposition in accordance with claim 29 wherein the polyolefin ispolypropylene.
 31. An olefin polymer composition in accordance withclaim 29 wherein the polyolefin is polyethylene.
 32. Anacrylonitrile-butadiene-styrene terpolymer having improved resistance todeterioration when exposed to light comprisingacrylonitrile-butadiene-styrene terpolymer and an alkylidene bisphenolphosphite or phosphate in accordance with claim
 1. 33. A polyurethaneresin composition having improved resistance to deterioration whenexposed to light comprising a polyurethane resin and an alkylidenebisphenol phosphite or phosphate in accordance with claim
 1. 34. A lightand heat stabilizer composition for improving the resistance todeterioration of synthetic polymers comprising an alkylidene bisphenolphosphite or phosphate in accordance with claim 1; and a syntheticpolymer heat stabilizer selected from the group consisting of phenolicantioxidants, polyvalent metal salts of organic acids, organicphosphites, thioethers and thiodipropionic acid esters.
 35. A light andheat stabilizer composition according to claim 34 in which the phenolicantioxidant has the formula: ##STR143## R is selected from the groupconsisting of hydrogen; halogen; and organic radicals containing fromone to about thirty carbon atoms, such as alkyl, aryl, alkenyl, alkaryl,aralkyl, cycloalkenyl, cycloalkyl, alkoxy, and acyl ##STR144## where R'is aryl, alkyl or cycloalkyl; x₁ and x₂ are integers from one to four,and the sum of x₁ and x₂ does not exceed six.
 36. A light and heatstabilizer composition according to claim 34 in which the phenolicantioxidant has the formula: ##STR145## wherein Y is a polyvalentlinking group selected from the group consisting of oxygen; carbonyl;sulfur; sulfinyl; aromatic, aliphatic and cycloaliphatic hydrocarbongroups; and oxyhydrocarbon, thiohydrocarbon and heterocyclic groups. Thelinking group can have from one up to twenty carbon atoms;Ar is aphenolic nucleus which can be a phenyl or a polycarbocyclic group havingcondensed or separate phenyl rings; each Ar group contains at least onefree phenolic hydroxyl group up to a total of five. The Ar rings canalso include additional rings connected by additional linking nuclei ofthe type Y, for example, Ar--Y--Ar--Y--Ar; m₁ and m₂ are numbers fromone to five, and n₁ and n₂ are numbers of one or greater, and preferablyfrom one to four.